JPH05222044A - Preparation of 2equivalent pyrazolotriazol magenta coupler - Google Patents

Abstract

PURPOSE: To simply and easily produce the subject compd. useful in a color photographic chemistry area by allowing a hydrazone to react with a halogen and a base and moreover allowing the obtained reaction mixture to react with a tert. amine.

CONSTITUTION: A compd. expressed by formula I (R is a 1-20C alkyl or aryl; (n) is 0-6) is allowed to react with a halogen and a base by two methods in a suitable solvent preferably. Chlorine or bromine is allowed to react with the compd. expressed by the formula I in the presence of the base by using a sodium salt of carboxylic acid as the base or the halogen is allowed to react with the compd. expressed by formula I in a solvent such as methylene chloride by using a tert. amine as the base. The objective compd. expressed by formula II (X is Cl or Br) is obtained by allowing the obtained reaction mixture to react with the tert. amine. The compd. is obtained without containing many steps, using a sulfur-containing intermediate and a fear of contamination due to elemental sulfur.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to 1H-pyrazolo [3,2-
The present invention relates to a novel method for producing a C] -S-triazole ring.

[0002]

[Chemical 3]

[0003]

2. Description of the Related Art As described in Research Disclosure 12443, Japanese Patent Publication Nos. 61/144647 and 62/195366, pyrazolo [3,2-C] -S-
Several methods are known in the art for the synthesis of triazole magenta couplers. For example, in order to produce a pyrazolo [3,2-C] -S-triazole magenta coupler, heat of a sulfur atom from S-triazolo [3,3-b] [1,3,4] thiadiazines accompanied by ring condensation Ejection is commonly used. This method is difficult and somewhat dangerous (Research Disclosure 12443
And other references cited above).

Another method for producing 1H-pyrazo [3,2C] -S-triazole by ring-closing, followed by saponification of a carboxylic acid ester functional group and decarboxylic acid [J. Ba.
iley et al ., J. Chem . Soc . Perkin, Trans. 1,2047 (1977); U.S. Patent No. 3,725,067 and East German Patent No. 26.
No. 3,060) is also known.

[0005]

These prior art methods are long and costly methods. These methods pose photographic and, at the same time, ecological challenges due to the use of relatively toxic intermediates and the use of sulfur materials.

[0006]

The method of the present invention comprises a hydrazone:

[Chemical 4] With a halogen and a base, preferably in a suitable solvent. The method can be carried out in two ways: (a) using the sodium salt of a carboxylic acid as the base, or (b) using a tertiary amine as the base. In (a), elemental chlorine or bromine is reacted with (I) in the presence of a base (preferably dissolved in an aqueous solution of the corresponding carboxylic acid). In (b), the elemental halogen is reacted with (I), preferably in a solvent such as methylene chloride, and then the reaction mixture thus formed is reacted with a base.

Thus, it can be seen that the present invention provides two types of means, both of which can be carried out using only a single reactor.

The present invention has many advantages over the prior art. First, compared to the method disclosed in Research Disclosure 12443, the operation of the present invention is simpler and safer to carry out. Secondly, compared to the other prior art mentioned above, the method of the present invention does not require post-saponification and decarboxylic acid post-steps to produce photographic couplers. Third, the method of the present invention contains no sulfur intermediates; therefore, there is less risk of contaminating photographic systems with elemental sulfur (elemental sulfur is known to adversely affect photographic emulsion speed).

Embodiments The present invention is a method for producing a pyrazolotriazole coupler, which comprises

[Chemical 5] With halogen and a base, said halogen being chlorine or bromine, said base being (i) an alkali metal salt of a lower alkylcarboxylic acid or (ii) a tertiary amine,

When the base is the alkali metal salt, the halogen is reacted with the compound (I) in the presence of the base, and when the base is the tertiary amine, the halogen is Reaction with compound (I) and then the reaction product thus formed is reacted with said tertiary amine, whereby said pyrazolotriazole coupler:

[0011]

[Chemical 6] Wherein said X is Cl or Br, n in said formula is an integer from 0 to about 6 and each R in said formula is the same. Or a manufacturing method characterized by being selected from alkyl or aryl groups which are different and have up to about 20 carbon atoms.

As described above, the compound of formula (I) is used in the method of the present invention. There are two subclasses of these compounds: in one subclass, n equals zero, and in other subclasses, n is a small integer from 1 to about 6. Compounds of both subclasses are prepared using conventional techniques with the appropriate hydrazine (or hydrazine hydrohalide salt, eg hydrochloride salt):

[0013]

[Chemical 7] The aldehyde:

[0014]

[Chemical 8] It can be produced by reacting with. When using a hydrohalide salt of hydrazine, a base such as a tertiary amine is used to bond with a hydrogen halide as a by-product. The compound (I) is preferably produced in a solvent such as methylene chloride, chloroform, acetic acid or a chlorinated organic solvent. Mild temperature, ie -5
-30 ° C, ambient pressure and reaction time of 0.5-5.0 hours are used.

In the process of the present invention, compound (I) is reacted with halogen, preferably chlorine or bromine. When using bromine, it is preferable to carry out the reaction using glacial acetic acid as a solvent. When chlorine is used, it is preferable to use methylene chloride as the solvent. The nature of the solvent is not limited, and other solvents that are inert to the reactants and products and have sufficient solvency to dissolve them can also be used. Examples of other suitable solvents include ether, tetrahydrofuran, dioxane.

The reaction can be carried out in the presence of salt from the beginning. If it is desirable to use this means,
The base is an alkali metal salt of a carboxylic acid (where the metal is L
It is preferably i, Na or K and the acid component is a lower alkyl monocarboxylic acid group, for example an acid component having 1 to about 4 carbon atoms and one carboxylic acid group). Thus, the preferred salt is R'COOM, where M is an alkali metal as defined above and R'is hydrogen or an alkyl group of up to about 3 carbon atoms. The preferred metal salt used as a base in the present invention is acetate, and the most preferred base of this type is sodium acetate.

When the reaction is carried out in the presence of such a base, it is preferable to use a solvent having an appropriate dissolving power for such a base. The preferred solvent for this reaction means is the acid, R'COOH, where R'has the meaning specified above. Thus, the preferred type of solvent is a lower carboxylic acid; most preferably an acid having the same anion as the base. Accordingly, acetic acid is the preferred solvent and is the solvent of choice when the compound of formula (I) is reacted with chlorine or bromine in the initial presence of a salt such as sodium acetate.

The method of the present invention need not be carried out in the presence of a base from the beginning. As mentioned above, the compound of formula (I) can be reacted with a halogen followed by the addition of a base to the reaction mixture to complete the reaction. The base need not be an alkali metal salt, such as those discussed above. That is, it may be another type of base, such as a tertiary amine. The nature of the amine itself is not limited, and pyridine, diethylenetriamine, triethylenediamine, or an amine of the formula NR "R" R "(each R" may be the same or different, preferably a lower alkyl group, For example, selected from alkyl groups having 1 to 4 carbon atoms) can be used. Three
It is further preferred that all R "groups are the same. Trimethylamine can be used, but its use is not preferred as it is a gas under normal conditions. Triethylamine is the preferred tertiary amine.

When an amine is used as the base, the solvent used is preferably not an acid. The solvent is preferably inert to the base and other components in the reaction system including the target product. Methylene chloride is the preferred solvent when the base (eg, amine) is added after contacting the halogen with the compound of formula (I) under reaction conditions.

The process of the invention is preferably carried out at ambient pressure. The process of the present invention is also usually carried out at a temperature of about -15 ° C to about 150 ° C, more preferably about -10 ° C to about 40 ° C.
The reaction time depends somewhat on the reaction temperature; the higher the temperature, the faster the reaction time. Generally, the compound of formula (II) is formed from the compound of formula (I) according to the present invention within about 0.5 to about 5.0 hours.

Reactants, ie halogen and formula (I)
The starting materials of 1 react with a molar ratio of 1: 1. However, it is not necessary to contact the reactants in this molar ratio and either reactant can be used in excess. In general, a moderate excess of halogen is used to increase yield. If desired, chlorine or bromine can be used in an amount of 1.1 to 3.0 mol per mol of the compound of formula (I). Greater or lesser amounts of halogen than this amount can be used.
If desired, excess halogen can also be removed prior to treatment of the product, for example by removing chlorine using a partial vacuum.

The following examples are intended to be illustrative of the present invention and not to limit the present invention.

[0023]

[Chemical 9]

Preparation of Hydrazone 3 18.51 in 120 mL of methylene chloride cooled to -5 ° C.
g (0.1 mole) of hydrazine hydrochloride 1 slurry,
20.2 g (0.2 mol) of triethylamine was added. The slurry was warmed to room temperature and 10.62 g (0.1 mol) of benzaldehyde was added in one portion. A clear orange solution was immediately obtained. This was stirred overnight at room temperature. The solvent was removed under vacuum. The solid thus obtained was stirred in 1 L of water for 3 hours. The solid was collected. It was washed with water and dried under vacuum. The weight of the obtained solid was 16.8 g (8
4%). The desired structure 3 according to the spectroscopic analysis data
Was confirmed.

Preparation of Coupler 4 Hydrazone 3 (2.01 g, 0.01 mol) and sodium acetate (0.984 g; 0.012 mol) were suspended in glacial acetic acid (30 mL), then bromine in 15 mL glacial acetic acid. (1.92 g; 0.012 mol) was added dropwise. After the addition is complete, the reaction mixture is stirred for 90 minutes at room temperature, then 100
Warmed at 25 ° C for 25 minutes. Upon cooling, the reaction mixture was poured into 500 mL cold water with stirring. Collecting the resulting precipitate,
It was washed with water and then vacuum dried. The crude material was chromatographed using a short column of silica gel. The purified material gave satisfactory analytical data: Yield of 4 was 1.11.
It was g (40%).

[0026]

[Chemical 10]

18.51 g in a 500 mL, 3-neck round bottom flask equipped with a magnetic stirrer, nitrogen inlet and addition funnel.
(0.1 mol) of 3-Mechirupirazoron - (5) - put of CH ₂ Cl ₂ hydrochloride 1 and 250 mL.
20.20 g (0.2 mol) was added to the obtained yellow slurry.
TEA (triethylamine) was gradually added. This slurry dissolved. Then 13.42 g (0.1 mol)
Of hydrocinnamaldehyde was added dropwise. After the addition, the reaction was stirred overnight. TLC (thin layer chromatography) showed the reaction was complete. Water was added. The organic product was extracted with CH ₂ Cl ₂ . The organic phase was dried and concentrated. An off-white solid was obtained. According to TLC
The presence of one spot of material was indicated. The spectroscopic data confirmed the desired structure. Yield of ( 5 ) is 20g
(88%).

A 250 mL, 3-neck round bottom flask equipped with a thermometer, N ₂ inlet and magnetic stirrer was charged with hydrazone ( 5 ).
2.283 g (0.01 mol) and anhydrous CH ₂ Cl ₂ 4
0 mL was added. The stirred slurry was cooled to -10 ° C (ice and salt bath). Chlorine gas was bubbled into the slurry. The solid gradually dissolved to give a dark red solution. The reaction temperature was kept at -10 ° C during the reaction with chlorine. After bubbling chlorine through, the solution was stirred for a further 20 minutes at -10 ° C. The reaction was then left to warm to room temperature. According to TLC, all starting material had disappeared. Excess chlorine and solvent were removed in vacuo.

CH ₂ Cl ₂ 50 was added to the resulting brown semi-solid.
mL was added to dissolve the solid. It was cooled to -10 ° C. Then 2.21 g TEA in 5 mL CH ₂ Cl ₂
(0.022 mol) was added dropwise. The reaction temperature was kept at -5 ° C. After the addition, the reaction was allowed to warm slowly to room temperature. The mixture was further stirred at room temperature for 40 minutes. The reaction was complete by TLC. The solvent was removed in vacuo. Ligroin was added to the resulting brown solid. The mixture was stirred for 30 minutes. The solid was collected and sucked dry. Then water 200
Stir in mL for 20 minutes. The solid was collected and dried. TL
According to C, the substance was substantially 1 spot. Rapid silica gel column chromatographic purification of the crude material gave 1.56 g of the desired coupler. The analytical data confirmed the desired structure ( 7 ).

Following the above examples, compounds of formula (II) having the structures shown in the following table can be prepared. For the purpose of omission, the formula (II) is modified to some extent so that the formula (IIA) (in the formula, R ²
Is a symbol substituted or used in formula (II)
(CH ₂ ) _n —R):

[0031]

[Chemical 11]

Non-limiting examples of compounds of formula IIA of the present invention are shown below.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

As will be apparent from the above discussion, the present invention involves the preparation of compounds in which the substituents are on a heterocyclic ring system.

In addition to fused rings, these products contain inert substituents attached to carbon atoms within the heterocycle, as shown.

For purposes of this invention, an "inert substituent".
Alternatively, an inert organic group is defined by having the following properties: (1) Stable or substantially stable under the reaction conditions used, ie it does not decompose to an undesired extent in the process used in the invention. thing.

(2) Non-reactive or substantially non-reactive with other reagents used for producing the compound of the present invention; that is, other components used for producing the compound of the present invention, Do not cause unrelated side reactions (to an unacceptable degree).

(3) Do not interfere with the production of the compound of the present invention by steric hindrance or other mechanism or effect.

Accordingly, a wide range of substituents may be included in the product. In other words, the present invention is not limited to the type of substituents as long as the substituents meet the criteria (1), (2) and (3). Typically, these groups are hydrogen or hydrocarbyl groups, ie groups composed exclusively of carbon and hydrogen. However, these need not consist solely of carbon and hydrogen;

[0042]

[Chemical 12]

--NH ₂ , NHR ₁ , NR ₁ R ₁ , --SO
_{2 -, - S -, -} S-S- , and alkoxy, groups consisting of aryloxy, etc. as long as these substituents meets the three criteria mentioned above, may be present in the present compound. Alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl and aryl groups meeting the above criteria may be present in the compounds of the present invention. These may be hydrocarbyl groups, or substituted hydrocarbyl groups, as discussed above. For convenience, R ₁ and R ₂
Are usually hydrogen or hydrocarbyl groups of up to about 20 carbon atoms; preferably they are hydrogen or alkyl or aryl groups of this type. Lower alkyl radicals (alkyl radicals having up to about 4 carbon atoms) and phenyl radicals are highly preferred.

The R ₃ radicals are generally selected by the nature they impart to the compound and / or the role they play in the chosen application.

On the other hand, the size or nature of the groups may be selected, or the physical or chemical nature of the group, eg, to a desired degree, as it is prepared in a convenient reaction to prepare the pyrazolotriazole starting compound. The groups may be selected to provide solubility or the desired degree of miscibility with the other ingredients of the mixture in which the product is used.

In addition, one or more of the radicals may be selected to contain a radical containing a reactive site. For example, R ² has the formula:

[Chemical 13] Wherein n is an integer equal to 0 to about 6 and the nitro group is ortho, meta or para to the alkyl side chain,
May be a group having Depending on the application, it may be desirable to reduce the aryl nitro group to an amino group. Therefore,
It is understood that the term "inert" in the phrase "inert substituent" does not mean that the substituent is non-reactive in the process carried out after the compound was formed.

[0047]

[Additional Embodiment]

1. The method according to claim, wherein n is equal to 0. 2. The method of Embodiment 1 wherein the halogen is bromine and the base is sodium acetate.

3. formula:

[Chemical 14] By reacting the compound of formula:

[Chemical 15] The method of Embodiment 2 wherein the compound of claim 2 is produced. 4. The method of claim 1 wherein n is equal to 1 to about 6.

5. The method of Embodiment 4 wherein the base is triethylamine. 6. formula:

[Chemical 16] Reacting the compound of with chlorine and then reacting the halogenated intermediate thus produced with triethylamine,
Thereby the coupler:

[0050]

[Chemical 17] The method of Embodiment 5 for producing

[0051]

INDUSTRIAL APPLICABILITY The method of the present invention is simple and easy to carry out, does not include many steps as in the prior art, does not use a sulfur-containing intermediate, or does not generate elemental sulfur pollution. As such, the method represents a significant advance in the art and at the same time appears to be suitable for industrial adoption.

The invention has been described with particular reference to the preferred embodiments. Those of ordinary skill in the art who are familiar with the above detailed description,
Additions or substitutions may be made without departing from the scope or spirit of the invention.

Claims (1)

[Claims] 1. A method for producing a pyrazolotriazole coupler, said method comprising: Is reacted with a halogen and a base, wherein the halogen is chlorine or bromine, the base is (i) an alkali metal salt of a lower alkylcarboxylic acid or (ii) a tertiary amine, and the base is the alkali metal. If a salt, the halogen is reacted with the compound (I) in the presence of the base, and if the base is the tertiary amine, the halogen is reacted with the compound (I), The reaction product thus formed is reacted with the tertiary amine, whereby the pyrazolotriazole coupler: Wherein said X is Cl or Br, n in said formula is an integer from 0 to about 6 and each R in said formula is the same. Or a process characterized by being selected from alkyl or aryl groups which are different and have up to about 20 carbon atoms.